湿度变化对交替3D打印试件微结构及力学性能的影响研究

本文提出一种全新的硅酸盐水泥(PC)与碱激发矿渣(AAS)交替3D打印工艺,并基于该工艺打印了硅酸盐水泥-碱激发矿渣复合试件。在试件干燥前后,分别采用X射线断层扫描成像技术(CT)分析了各复合试件以及碱激发矿渣打印试件的微观结构,并测试了各试件干燥前后的抗折与抗压强度。结果表明,碱激发矿渣与硅酸盐水泥的抗干缩性能不同,在内部湿度下降时,两种材料的打印界面容易因干缩不一致而开裂,引起打印成品微结构劣化以及力学性能下降。尽管如此,采用交替3D打印工艺,硅酸盐水泥有效弥补了碱激发矿渣强度的不足,打印成品的抗折与抗压强度均高于碱激发矿渣打印试件。对比逐层交替与逐列交替两种3D打印方法,逐层打印试件的抗折强度更高,而逐列打印试件的抗压强度更高。上述研究成果对3D打印混凝土技术的推广运用有一定指导意义。     

3D printing ceramic cores for investment casting of turbine blades,using LCD screen printers: The mixture design and characterisation

The primary objective of this study is to demonstrate the possibility of developing silica, alumina, and zircon-based photocurable ceramic suspensions that can be used for visible light photopolymerization (> 450 nm) and to optimise the binder formulations for the purpose of LCD-based ceramic 3D printing applications. Reference ceramic components for this work are ceramic cores employed in the investment casting of high-pressure turbine blades and vanes. Arguably, one of the most critical steps in photoinduced ceramic 3D printing is developing suitable ceramic suspensions, having high ceramic loading, low viscosity, and short curing times. Ceramic suspensions with four different novel binder formulations and commercial ceramic powders used in core manufacturing (SiO₂, Al₂O₃ and ZrSiO₄) were investigated to achieve the best trade-off between: (1) their curing performance (cure depth and curing speed), (2) rheological properties of the binder mixtures at the solid loadings of 60 vol.% for SiO₂, 55 vol.% for ZrSiO₄, and 45 vol.% for Al₂O₃; and (3) the green body mechanical properties of the mixtures after printing. The effect of ceramic particles on the selected binders was examined individually, and the correlation between cure depth (C_d), volumetric loading, and curing speed are evaluated. The results show all binders designed in this study provide an adequate cure depth, even at high ceramic loadings. When the curing behaviour of all unloaded binder mixtures from the previous study [1] compared with the 10 vol.% SiO₂ loaded mixtures, the cure depth of all formulated binder mixtures increased 50–55 % and the curing thickness of 60 vol.% SiO₂ loaded suspensions were still slightly higher than their unloaded counterparts. The rheology outcomes indicate that lower viscosity binders always result in lower viscosity of the ceramic loaded inks, even without taking the effect of dispersants into account. Besides, the addition of N-Vinyl-2-Pyrrolidone (NVP) monofunctional monomer to the binder mixtures significantly reduces the viscosity and changes the normally linear relationship of the mix viscosity and its silica loading content. Among the binder formulations loaded with 60 vol.% of SiO₂, the formulation providing the lowest viscosity and highest mechanical property consists of 5 wt.% of NVP, 45 wt.% of HDDA and 50 wt.% of Photocentric 34 resin. Although this binder mixture showed the highest green flexural strength when loaded by 55 vol.% ZrSiO₄, all other mixtures loaded with zircon flour also demonstrated a near-fluid behaviour, below 200 s^?1. In Al₂O₃ loaded mixtures, the HDDA di-functional binder formulations present lowest viscosity and the di- and multifunctional monomer blends (HDDA-Photocentric27) showed the highest mechanical properties when used in a 50/50 ratio. This work summarises the best binder choices for silica, alumina and zircon based ceramic suspensions used in core printing for investment casting applications through LCD screen printing.     

Nanomaterials for 3D Printing of Polymers via Stereolithography: Concept,Technologies, and Applications

Stereolithography (SLA) is an additive manufacturing method with one of the highest accuracies (down to 100 nm) of all solid freeform techniques and has been used in various areas, such as medicine, automotive, aerospace, electronics, and others. However, most resins available nowadays are derived from petroleum. Its toxicity, low biocompatibility, and growing environmental concerns are limiting its application. This review discusses the development of biobased and biocompatible materials for different SLA processes as well as the usage of nanocomposites to increase their applicability. A comprehensive overview of the SLA technologies, photopolymerization chemistry, and resin properties are also provided. Finally, various examples using different types of materials are explored, to show the current and future capabilities of the SLA technique.     

Cellular,Mineralized, and Programmable Cellulose Composites Fabricated by 3D Printing of Aqueous Pastes Derived from Paper Wastes and Microfibrillated Cellulose

Combining recycling of paper wastes (WPs) with extrusion‐based additive manufacturing represents a sustainable route to cellular cellulose composites tailored for lightweight construction. Particularly, shear mixing of shredded WPs with an aqueous solution of a polymer binder like polyvinyl alcohol (PVA) yields aqueous pastes suitable for 3D printing. As a shear thinning additive, both WP and microfibrillated cellulose account for enhanced shear thinning and dimensional stability. Opposite to the formation of dense WP/PVA composites by melt extrusion, 3D printing of aqueous pastes produces cellular cellulose/PVA composites exhibiting hierarchical pore architectures. In spite of low densities around 0.8 g cm^?3, high Young's modulus (2.0 GPa) and tensile strength (53 MPa) are achieved. Mechanical stability, water resistance, and even flame retardancy simultaneously improve by crosslinking with glyoxal and especially by mineralization. Multimaterial 3D printing combines the 3D dispensing of cellulose/PVA pastes with the simultaneous, staged, or subsequent spraying of aqueous water glass to enable mineralization of composite surface, bulk, and interlayers. Furthermore, the glyoxal‐mediated crosslinking affords thermo‐ and moisture‐responsive cellulose/PVA composites with programmable shape change induced either by heating at 100 °C or by exposure to moisture at 37 °C.     

Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

The use of self‐assembling, pre‐polymer materials in 3D printing is rare, due to difficulties of facilitating printing with low molecular weight species and preserving their reactivity and/or functions on the macroscale. Akin to 3D printing of small molecules, examples of extrusion‐based printing of pre‐polymer thermosets are uncommon, arising from their limited rheological tuneability and slow reactions kinetics. The direct ink write (DIW) 3D printing of a two‐part resin, Epon 828 and Jeffamine D230, using a self‐assembly approach is reported. Through the addition of self‐assembling, ureidopyrimidinone‐modified Jeffamine D230 and nanoclay filler, suitable viscoelastic properties are obtained, enabling 3D printing of the epoxy–amine pre‐polymer resin. A significant increase in viscosity is observed, with an infinite shear rate viscosity of approximately two orders of magnitude higher than control resins, in addition to, an increase in yield strength and thixotropic behavior. Printing of simple geometries is demonstrated with parts showing excellent interlayer adhesion, unachievable using control resins.     

3D打印在催化和吸附材料制备领域的应用

3D打印是一种快速成型技术,该技术在催化和吸附材料制备领域的应用目前已受到广泛重视。3D打印技术一方面能够拓展整体式催化/吸附材料的涵盖范围,实现材料的宏观结构优化和活性组分控制,同时有利于强化催化和吸附过程中的传质/传热过程,而且操作灵活,可靠性强,因此适于工业生产和实验室研究。本文介绍了催化/吸附材料制备过程中常见的几种3D打印技术,同时从打印策略和打印材料方面入手,综述了目前3D打印技术在催化和吸附领域的各项应用,并由此指出,目前3D打印技术可以将聚合物、碳材料、金属及金属氧化物、分子筛等材料纳入到整体式催化体系中,通过对材料结构和分布的控制对其催化和吸附性能进行影响,因此3D打印在催化和吸附材料制备领域的应用有着广阔的前景。同时指出材料微观结构控制、打印耗材及流程的标准化,以及以计算为依托的催化/吸附材料的整体式结构和活性位点分布控制是今后的研究重点。     

Epoxy Doped,Nano-scale Phase-separated Poly-Acrylates with Potential in 3D Printing

An efficient method to improve the mechanical performance of a commercially available photocure resin is described wherein the resin is modified with a mixture of a cycloaliphatic epoxy and an anhydride curing agent. Photocured samples are thermally treated in a subsequent step to cure the epoxy to obtain an interpenetrated polymer network (IPN) and also complete reaction of the acrylate monomers remaining from the photocure. The latter is accomplished by a thermal radical initiator added earlier into the formulation together with the epoxy-anhydride. The thermal properties and microstructure of the resulting IPN are analyzed. Uniform and quantitative conversions are obtained, with glass transition temperatures comparable to conventional epoxies. The liquid, uncured samples containing different amounts of epoxy are stable at 30 °C for several weeks. In the fully cured epoxy-rich materials, nano-scale phase separation is observed by atomic force microscopy. This is corroborated by the existence of multiple relaxations determined by dynamic mechanical analysis analysis. Specimens from a formulation containing 50% by weight of epoxy-anhydride are 3D printed in a customized masked image processing stereolithography, thermally treated, and are subjected to compression tests. Results show that Young's modulus increases by 900% over the neat resin.     

Impact of processing conditions and sizing on the thermomechanical and morphological properties of polypropylene/carbon fiber composites fabricated by material extrusion additive manufacturing

For the 3D printed composites, fiber alignment is affected by the direction of melt-flow during extrusion of filaments and subsequently through the printing nozzle. The resulting fibers orientation and the fiber-matrix compatibility have a direct correlation with mechanical properties. This study investigates the impact of processing conditions on the state of the carbon fiber types and their orientation on the mechanical properties of 3D-printed composites. Short and long carbon fibers were used as starting reinforcing materials, and the state of fibers at the beginning and on the printed parts were evaluated. Strong anisotropy in terms of mechanical properties (flexural and impact properties) was observed for the samples printed with different printing orientations. Interestingly, the number of voids in the printed composites was found to be correlated with the fiber types. The present work provides a step towards the optimization of tailored composite properties by additive manufacturing.     

Low‐Viscosity Limonene Dimethacrylate as a Bio‐Based Alternative to Bisphenol A‐Based Acrylic Monomers for Photocurable Thermosets and 3D Printing

Bisphenol A glycidyl methacrylate (BisGMA) is well established as photocurable resin in dental restoratives and 3D printing. At present there are raising concerns regarding the estrogen‐mimicking bisphenol A (BPA) contamination of health care and consumer products. It is an important challenge to substitute BPA‐based resins for bio‐based cycloaliphatic monomers while lowering resin viscosity without sacrificing high stiffness and glass temperature. Particularly high viscosity is critical for 3D printing by photopolymerization. Unlike BPA the cyclic monoterpene limonene, extracted from citrus fruit peels, is safe in human uses. Herein it is reported on limonene‐based dimethacrylate (LDMA) tailored for 3D printing application and derived from limonene oxide (LO) and methacrylic acid (MA). Residual MA is converted into glycerol dimethacrylate (GDMA) serving as an in situ reactive diluent. The influences of temperature, catalysts, MA/LO stoichiometry, and the addition of glycidyl methacrylate (GMA) and magnesium oxide on the LDMA‐based resin performance are elucidated. As compared to BisGMA (560 Pa s) LDMA‐based resins exhibit significantly lower viscosity (5–117 Pa s) governed by the MA/LDMA molar ratio and the GMA addition. At 30 wt% LDMA content photocured resin yields thermosets having high Young’s Modulus (3.4–3.7 GPa), tensile strength (88–98 MPa), and glass transition temperature (119–135 °C), surpassing the performance of the corresponding BisGMA‐based resins.     

3D Printing of a Robust Polyamide‐12‐Carbon Black Composite via Selective Laser Sintering: Thermal and Electrical Conductivity

The need for big volume powder materials in building mechanically robust sintered parts via selective laser sintering (SLS) has been observed considering the direction towards the future of mass fabrication. This work presents a facile approach of combining polyamide‐12 (PA12) and carbon black (CB) powders to be used in the SLS application. The study investigates the mixing consistency, mechanical property, and thermal stability changes of the resulting 3D printed material. Bulk resistivity is correlated with the amount of CB, showing consistency of carbon content in the sintered parts produced by the effective separate grains mixing method. 3D printed parts are built with 0, 1.5, 3, 5 and 10 wt% CB via SLS. Improvements are seen at 1.5 and 3 wt% CB with the blockage of crack growth by the CB particles on applied load. For concentrations greater than 3 wt%, mechanical properties degrade due to hindering of physical contact between PA12 particles caused by CB particles, thereby reducing the effectiveness of the sintering process. The CB/PA12 sintered parts exhibit enhanced thermal stability resulting in higher degradation temperatures than the neat PA12. Therefore, in this study, thermally and mechanically enhanced 3D printed CB/PA12 build parts via SLS are successfully demonstrated.     

Biocompatibility and Biological Performance Evaluation of Additive-Manufactured Bioabsorbable Iron-Based Porous Suture Anchor in a Rabbit Model

This study evaluated the biocompatibility and biological performance of novel additive-manufactured bioabsorbable iron-based porous suture anchors (iron_SAs). Two types of bioabsorbable iron_SAs, with double- and triple-helical structures (iron_SA_2_helix and iron_SA_3_helix, respectively), were compared with the synthetic polymer-based bioabsorbable suture anchor (polymer_SAs). An in vitro mechanical test, MTT assay, and scanning electron microscope (SEM) analysis were performed. An in vivo animal study was also performed. The three types of suture anchors were randomly implanted in the outer cortex of the lateral femoral condyle. The ultimate in vitro pullout strength of the iron_SA_3_helix group was significantly higher than the iron_SA_2_helix and polymer_SA groups. The MTT assay findings demonstrated no significant cytotoxicity, and the SEM analysis showed cells attachment on implant surface. The ultimate failure load of the iron_SA_3_helix group was significantly higher than that of the polymer_SA group. The micro-CT analysis indicated the iron_SA_3_helix group showed a higher bone volume fraction (BV/TV) after surgery. Moreover, both iron SAs underwent degradation with time. Iron_SAs with triple-helical threads and a porous structure demonstrated better mechanical strength and high biocompatibility after short-term implantation. The combined advantages of the mechanical superiority of the iron metal and the possibility of absorption after implantation make the iron_SA a suitable candidate for further development.     

Challenges in particle size distribution measurement past, present and for the 21st century

The field of particle size distribution (PSD) characterization and measurement has experienced a renaissance over the past ten years. This revitalization has been driven by advances in electronics, computer technology and sensor technology in conjunction with the market pull for PSD methods embodied in cost effective user friendly instrumentation. The renaissance can be characterized by at least four activities. (1) End user innovation exemplified by techniques such as hydrodynamic chromatography (HDC), capillary hydrodynamic fractionation (CHDF) and field flow fractionation methods (SdFFF, FlFFF, and ThFFF). (2) Revitalization of older instrumental methods such as gravitational and centrifugal sedimentation; (3) Evolution of research grade instrumentation into low cost, routine, user friendly instrumentation exemplified by dynamic light scattering (DLS). (4) The attempt to meet extremely difficult technical challenges such as: (a) providing a single hybrid instrument with high resolution over a very broad dynamic range (4+ decades in size; e.g., Fraunhofer/Mie; photozone sensing/DLS); (b) PSD measurement of concentrated dispersions (acoustophoretic, dielectric measurements, fiber optic DLS (FOQELS)); (c) in-situ process particle size sensors (in-line or at line, e.g., FOQELS); (d) routine measurement of particle shape and structure (e.g., image analysis). Instrumental methods resulting from these activities are discussed in terms of measurement principles and the strengths and weaknesses of these methods for characterizing PSDs. Business and societal driving forces will impact customer perceived instrumentation and knowledge needs for the 21st century and the ability to meet the specific difficult technical challenges in particle size distribution characterization mentioned above. Anticipated progress toward meeting these technical challenges is discussed in conjunction with the associated anticipated advances in required technologies.     

3D Printing to Increase the Flexibility of the Chemical Synthesis of Biologically Active Molecules: Design of On-Demand Gas Generation Reactors

The development of new drugs is accelerated by rapid access to functionalized and D-labeled molecules with improved activity and pharmacokinetic profiles. Diverse synthetic procedures often involve the usage of gaseous reagents, which can be a difficult task due to the requirement of a dedicated laboratory setup. Here, we developed a special reactor for the on-demand production of gases actively utilized in organic synthesis (C₂H₂, H₂, C₂D₂, D₂, and CO₂) that completely eliminates the need for high-pressure equipment and allows for integrating gas generation into advanced laboratory practice. The reactor was developed by computer-aided design and manufactured using a conventional 3D printer with polypropylene and nylon filled with carbon fibers as materials. The implementation of the reactor was demonstrated in representative reactions with acetylene, such as atom-economic nucleophilic addition (conversions of 19–99%) and nickel-catalyzed S-functionalization (yields 74–99%). One of the most important advantages of the reactor is the ability to generate deuterated acetylene (C₂D₂) and deuterium gas (D₂), which was used for highly significant, atom-economic and cost-efficient deuterium labeling of S,O-vinyl derivatives (yield 68–94%). Successful examples of their use in organic synthesis are provided to synthesize building blocks of heteroatom-functionalized and D-labeled biologically active organic molecules.     

Additive manufacturing of ceramics: Advances,challenges, and outlook

Additive manufacturing (AM) of ceramics is relatively more challenging with respect to polymers and metals, owing to their high melting temperatures and inherent brittleness. Thus, this review aims to provide a comprehensive survey of recent AM technologies successfully employed to produce net shape ceramic components. In recent years, several techniques have been developed and the latest progress in this field are highlighted, as well as the current challenges in the complex shaped ceramic parts production via AM technologies. The state of the art concerning the various 3D printing processes applied to the fabrication of ceramic components is discussed with, for each method, the presentation of its advantages, disadvantages, and possible applications. The potential of AM for producing complex shape ceramic components and the challenges to overcome are discussed as well.     

Optimizing the mechanical properties of TiO2/PA12 nano-composites fabricated by SLS 3D printing

In this paper, the selective laser sintering process was used to fabricate the TiO₂/PA12 nano-composite parts by considering the parameters of laser power, scanning speed, and TiO₂ content. The response surface methodology was used to improve the mechanical properties of TiO₂/PA12 nano-composite parts. The fracture surface characteristics of the specimens were examined using the scanning and transmission electron microscopy. The results indicated that the increase in laser power from 10 to 15 W improved the tensile strength, modulus, and impact strength of the nano-composite parts because of the fine dispersion of TiO₂ nano-particles. An increase in the scanning speed from 2000 to 3000 mm/s resulted in the reduction of tensile strength and modulus due to lower heat input and consequently incomplete densification of polyamide-12. In addition, the increase of TiO₂ content up to 5 wt% can improve the tensile strength, modulus, and impact strength, but requires increasing the laser power. However, the mechanical properties of the nano-composite parts were enhanced simultaneously at laser power of 12.4 W, scanning speed of 2000 mm/s and TiO₂ content of 1.9 wt%. Moreover, the addition of TiO₂ up to 5 wt% showed a slight influence on thermal stability and crystallinity of the sintered specimens.     

Microporosities in 3D-Printed Tricalcium-Phosphate-Based Bone Substitutes Enhance Osteoconduction and Affect Osteoclastic Resorption

Additive manufacturing is a key technology required to realize the production of a personalized bone substitute that exactly meets a patient’s need and fills a patient-specific bone defect. Additive manufacturing can optimize the inner architecture of the scaffold for osteoconduction, allowing fast and reliable defect bridging by promoting rapid growth of new bone tissue into the scaffold. The role of scaffold microporosity/nanoarchitecture in osteoconduction remains elusive. To elucidate this relationship, we produced lithography-based osteoconductive scaffolds from tricalcium phosphate (TCP) with identical macro- and microarchitecture, but varied their nanoarchitecture/microporosity by ranging maximum sintering temperatures from 1000 °C to 1200 °C. After characterization of the different scaffolds’ microporosity, compression strength, and nanoarchitecture, we performed in vivo studies that showed that ingrowth of bone as an indicator of osteoconduction significantly decreased with decreasing microporosity. Moreover, at the 1200 °C peak sinter temperature and lowest microporosity, osteoclastic degradation of the material was inhibited. Thus, even for wide-open porous TCP-based scaffolds, a high degree of microporosity appears to be essential for optimal osteoconduction and creeping substitution, which can prevent non-unions, the major complication during bone regeneration procedures.     

增材制造技术在火炸药成型中的研究进展

针对国内外火工品、炸药、发射药、推进剂增材制造技术,按照增材制造的技术特点和应用方向,综述了国内外增材制造技术在火炸药成型中的研究现状。概述了材料喷射成型(Material jetting)、材料挤出成型(Material extruding)、光聚合固化技术(Vat photopolymerization)的成型原理、工艺特点及在火炸药成型中的应用情况,介绍了各类增材制造技术中火炸药的物料特性,并对火炸药增材制造技术发展方向进行了预测。指出火炸药增材制造应按照火炸药的应用背景,对增材制造火炸药配方(即耗材)的能量特性、力学特性、能量释放特性及工艺适配性等进行系统研究,以满足不同应用背景的发展需求。附参考文献97篇。     

CO2 abatement in oscillating packed‐bed scrubbers: Hydrodynamics and reaction performances for marine applications

Gas‐liquid flow dynamics and CO₂‐monoethanolamine absorption performances of an oscillating countercurrent packed bed were analyzed by means of a transient 3D nonisothermal two‐fluid flow model with a goal to understand the behavior of scrubbing units on‐board floating production, storage and offloading platforms. Gas‐liquid flow deviation from axial symmetry was significant at larger vessel inclinations prompting noticeable liquid accumulation in the column lowermost area. Conversely, in static vertical and slightly inclined columns only a reduced fraction of the liquid was subject to transverse segregation. Externally‐generated column oscillations brought about complex secondary flows in radial and tangential directions resulting in oscillatory patterns with amplitude and propagation frequency affected by the packed bed oscillations. CO₂ abatement in inclined and asymmetrically oscillating columns suffered perceptible deviations with respect to vertical configuration while symmetrically oscillating columns gave rise to CO₂ performances oscillating around the steady‐state solutions of the vertical column. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1064–1076, 2017     

Synthesis, 3D‐QSAR,and Structural Modeling of Benzolactam Derivatives with Binding Affinity for the D2 and D3 Receptors

A series of 37 benzolactam derivatives were synthesized, and their respective affinities for the dopamine D₂ and D₃ receptors evaluated. The relationships between structures and binding affinities were investigated using both ligand‐based (3D‐QSAR) and receptor‐based methods. The results revealed the importance of diverse structural features in explaining the differences in the observed affinities, such as the location of the benzolactam carbonyl oxygen, or the overall length of the compounds. The optimal values for such ligand properties are slightly different for the D₂ and D₃ receptors, even though the binding sites present a very high degree of homology. We explain these differences by the presence of a hydrogen bond network in the D₂ receptor which is absent in the D₃ receptor and limits the dimensions of the binding pocket, causing residues in helix 7 to become less accessible. The implications of these results for the design of more potent and selective benzolactam derivatives are presented and discussed.     

Controlling Crystallization: A Key Factor during 3D Printing with the Advanced Semicrystalline Polymeric Materials PEEK,PEKK 6002, and PEKK 7002

Controlling the crystallization of advanced, high-performance polymeric materials during 3D printing is critical to ensure that the resulting structures have appropriate mechanical properties. In this work, two grades of polyetherketoneketone (PEKK 6002 and PEKK 7002) are used to print 3D specimens via a fused filament fabrication process. The samples are compared with polyetheretherketone printed under the same conditions. Two approaches for controlling the crystallization process are undertaken. The first involves adjustment of the chamber temperature between room temperature and 190 °C to create two regions where crystallization is governed by the slow diffusion process and elevated by limiting the nucleation process. The second approach involves selection of PEKK materials with varying crystallization kinetics, namely. Application of this method into 3D-printing process allows for printing semicrystalline materials with tailored mechanical, thermal, and chemical properties as either amorphous or in situ crystallized products. The studies undertaken here provide the basis to eliminate expensive and time-consuming post-processing of 3D fabricated parts. In particular, solutions for the avoidance of poor adhesion to the building plate and weak interlayer adhesion that can lead to warping are described. The materials are divided into three groups, slow, moderate, and too fast crystallization kinetics.